CN103904297A - Structures for interdigitated finger co-extrusion - Google Patents

Structures for interdigitated finger co-extrusion Download PDF

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CN103904297A
CN103904297A CN201310673712.5A CN201310673712A CN103904297A CN 103904297 A CN103904297 A CN 103904297A CN 201310673712 A CN201310673712 A CN 201310673712A CN 103904297 A CN103904297 A CN 103904297A
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structure according
rectangle
section
cross
interdigitated
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CN103904297B (en
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C·L·科布
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Palo Alto Research Center Inc
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Palo Alto Research Center Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0411—Methods of deposition of the material by extrusion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

An electrode structure has an interdigitated layer of at least a first material and a second material, the second material having either higher or similar electrical conductivity of the first material and being more ionically conductivity than the first material, a cross-section of the two materials being non-rectangular.

Description

For the structure of interdigitated coextrusion
Background technology
Exist wherein battery, fuel cell, electric interconnection, ultra-capacitor etc. to benefit from many application of interdigitated of the tight spacing of different materials.These materials can use coextrusion print head (having United States Patent (USP) 7,799, the similar but alternative print head shown in the 371) coextrusion described in U.S. Patent Publication 2012/0156364.Speech therefrom, is meant in the time that material flows by coextrusion, and material does not mix.But resulting structures has rectangular geometry under cross-sectional form, and in the direction perpendicular to interdigitated geometry, there is straight line and print uniformly.
Summary of the invention
But modeling has shown that non-rectangle cross-sectional geometry has performance raising gain aspect electric capacity and energy density.Conventionally, electrode derives from slit coating process or film and semiconductor fabrication.These methods do not reach the cost effectiveness of preparing on a large scale structured electrodes yet.
Brief description of the drawings
Fig. 1 has shown an interdigitated structure of prior art.
Fig. 2-3 have shown the embodiment of interdigitated structure.
Fig. 4 has shown a prior art embodiment of interdigitated structure.
Fig. 5-6 have shown the embodiment of interdigitated structure.
Fig. 7 has shown an embodiment of battery structure.
Fig. 8 and 9 has shown marking on a map for the stock utilization of the current embodiment of prior art and lithium structure.
Figure 10 has shown marking on a map of discharge performance between prior art and the current embodiment of lithium structure.
Figure 11 and 12 has shown the embodiment of the wavy pattern of extruded material.
Embodiment
Fig. 1-6 have shown use coextrusion print head (as United States Patent (USP) 7,799, shown in 371) and the various embodiment of structure that form.Fig. 1 has shown a prior art embodiment of electrode structure 10.Structure has with wider portion and cross one another the first material 12 of the second material 14.Material 12 is made up of closelypacked active electrode material, and material 14 is made up of for improving ionic conductivity or conductivity highly porous material.Material 14 can have the higher or identical conductivity of the first material, and more likely has higher ionic conductivity.
Fig. 4 has shown similar prior art scheme, different is region 34 must control oneself removed expendable material.Only there is compact area (as 32) to retain.In the embodiment of battery electrode, this will allow electrolyte fill area.
Fig. 2-3 have shown closelypacked region 18 and 24, and have the porous region 20 and 26 of non-rectangle cross section.By control procedure condition, as pressure adjusting, fluid flow and fluid rheology, can obtain structure 16 and 22.For fluid rheology, the viscosity of two materials should be with similar density matching.But due to the concentration of electric conducting material, density may be different, but the coupling of viscosity is still important.
The non-rectangle cross section in region 18 and 24 allows the concentration gradient in control electrode structure 16 and 22 better.These structures have the larger surface area in the tightly packed region that is exposed to porous region.Larger concentration gradient on battery electrode causes larger ohmic voltage drop, and this affects energy density and the power density of battery.By controlled concentration gradient, can avoid large gradient and increase the efficiency of battery.Non-rectangle cross section can have wedge angle or fillet.
Fig. 5 and 6 has shown similar structure 36 and 42, and they have the non-rectangular area 38 and 44 and such as 40 and 46 non-rectangle space of tightly packed material.In these structures, electrolyte will be filled in space, thereby the more high surface area of tightly packed material is exposed to electrolyte.
Fig. 7 has shown the simplification calcspar of battery model, and described battery model is for determining the improvement in performance of non-rectangle electrode cross-section than rectangular cross section embodiment.Structure 50 has current-collector border 52.In this embodiment, by thickness, the lithium paper tinsel in 50 micrometer ranges forms anode 54.Separator 56 separates anode 52 and cathode construction 58.In this embodiment, cathode construction 58 is made up of the graded area of tightly packed material and highly porous material.Although these regions are shown as rectangle by the calcspar of Fig. 7, in fact they have the shape of Fig. 2 and 3.In this embodiment, closelypacked region is made up of the cobalt-lithium oxide (LCO) of the active material of 70% concentration, and highly porous region is made up of the LCO of 40% concentration.
Material can be the battery material of any type of the active material concentration with any scope, but highly porous region has than compact area active material still less conventionally.In addition, material can be used for being different from other structures of battery.The example of spendable material comprises cobalt-lithium oxide (LCO), manganese oxide cobalt nickel lithium (NCM) or both mixtures.Other materials can comprise cobalt aluminum nickel lithium (NCA), manganese oxide lithium (LMO), ferric phosphate nickel (LFeP).Anode material can be lithium titanate (LTA).
Fig. 8 and 9 has shown respectively the marking on a map of stock utilization of the electrode structure of Fig. 1 and Fig. 2 after ' 1C ' electric discharge, and the current density wherein applying is 12.9mA/cm 2.' C ' speed electric discharge is battery measuring with respect to the speed of its maximum capacitor electric discharge.' 1C ' speed is the electric current that battery was emitted its whole electric capacity in 1 hour.Quality and volume conservation between porous region and the compact area of structure, the geometry that only difference is cross section.Under 1C speed, the structure of Fig. 2 has than the structure of Fig. 1 larger about 10% active material utilization.
Electric capacity, energy and power number in following table shown relative performance improvement instead of the attainable absolute improvement in performance of cobalt-lithium oxide between structure.Figure 10 has shown the energy, power and the electric capacity gain that use non-rectangle structure to obtain in conjunction with following table.In figure in Figure 10, the structure that the line of top is Fig. 2, the structure that the line of below is Fig. 1.The demonstration of marking on a map, than the structure of Fig. 1, the structure of Fig. 2 has longer running time and lower voltage drop.This is due to concentration gradient lower in the increase of active material utilization and cathode construction.
Figure BDA0000434918110000031
As previously mentioned, these gains do not come more volume or the larger quality of self-structure, and only from the change of geometry.
Up to the present, the geometry change concentrating on respect to the cross section of battery electrode structure is discussed.But as previously mentioned, the control of procedure parameter can realize the non-rectangle structure being formed by print head as etching mask and interconnection.In this case, the material staying when formation is removed expendable material by the structure shown in Fig. 5 and 6.Depend on the object of material in resulting structures, described material can be conduction or polymer.For example, for circuit interconnection, material is (metal or the conducting polymer) of conduction, and it is used as contact after removing expendable material.
Print head described in U.S. Patent Publication 2012/0156364 has so-called ' cleaning ' stream, and wherein the edge of stream and corner are angled and/or tilt, and may gather the dead point of part to reduce material.The described material gathering can reach critical mass and pour subsequently stream, or it can cause stream to shrink.In arbitrary situation, by cleaning stream, the uniformity that is deposited on lip-deep resulting materials keeps with straight monolithic pattern.But, by using the stream of ' not cleaning ', or by using pressure reduction or mechanical movement that material is flowed to pulse to print head, can form from the teeth outwards material more random, rise and fall or the flow pattern of ' wavy '.
Figure 11 has shown an example of this random patterns of material.Gained deposit is made up of the wavy lines of two kinds of different materials 62 and 64.As previously mentioned, can remove the one in material, it serves as expendable material.Can be filled by different materials by removing the hole staying.Or surplus material can form interconnection and contact pad, or can be formed for the etching mask of below material.
Figure 12 has shown the reduced form of patterns of material.Flow direction is defined as wherein material from the mobile direction of print head.Print head is advanced the edge of the pattern from approaching most observer, and retracts away from observer.With the orthogonal direction of the film vertical view that is film.Stacking direction refers to by move print head on multiple parallel paths, this patterned side to ' stacking ' with by shown in the patterned side compared with little is formed in direction to the ability of much bigger pattern to being stacked.
The electrode structure that in this way, can there is non-rectangle cross section by formation be formed for battery more effectively, more high performance electrode structure.Non-rectangle structure can be by control procedure parameter be formed by the existing print head with cleaning stream, or can be by being similar to existing print head but the print head with ' not cleaning ' path form.Similarly, can be used as interconnection or the disordered structure of random etching mask can use existing print head or use to have not clean the print head of stream to form by process control.

Claims (9)

1. an electrode structure, it comprises:
The interdigitated layer of at least the first material and the second material, described the second material has higher than or is similar to the conductivity of described the first material, and than more ionic conduction of described the first material, the cross section of described bi-material is non-rectangle.
2. structure according to claim 1, wherein said the second material comprises electrolyte.
3. structure according to claim 1, wherein said the first material is the one in cathode material or anode material.
4. structure according to claim 1, wherein said non-rectangle cross section has wedge angle.
5. structure according to claim 1, wherein said non-rectangle cross section has fillet.
6. structure according to claim 1, wherein said the second material is expendable material.
7. structure according to claim 1, wherein than described the first material, described the second material has higher porosity.
8. structure according to claim 1, wherein said interdigitated layer comprises the one in wavy or fluctuating pattern.
9. structure according to claim 1, wherein said interdigitated layer comprises straight monolithic pattern on print direction.
CN201310673712.5A 2012-12-27 2013-12-11 For the structure of interdigitated coextrusion Active CN103904297B (en)

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US13/727,937 US9899669B2 (en) 2012-12-27 2012-12-27 Structures for interdigitated finger co-extrusion
US13/727937 2012-12-27

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CN103904297B CN103904297B (en) 2018-06-01

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110278170A1 (en) * 2000-10-20 2011-11-17 A123 Systems, Inc. Battery structures, self-organizing structures and related methods
CN102646834A (en) * 2010-12-17 2012-08-22 帕洛阿尔托研究中心公司 Interdigitated electrode structure

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110278170A1 (en) * 2000-10-20 2011-11-17 A123 Systems, Inc. Battery structures, self-organizing structures and related methods
CN102646834A (en) * 2010-12-17 2012-08-22 帕洛阿尔托研究中心公司 Interdigitated electrode structure

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JP6581332B2 (en) 2019-09-25
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EP2749394A1 (en) 2014-07-02
KR102025069B1 (en) 2019-09-25
JP2014130810A (en) 2014-07-10
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